CN106866377A - A kind of ether bond rupture method of phenyl alkyl ether - Google Patents
A kind of ether bond rupture method of phenyl alkyl ether Download PDFInfo
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- C07C45/65—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups
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- C07C51/377—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
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Abstract
The invention discloses a kind of ether bond rupture method of phenyl alkyl ether, the method is：In organic solvent, under conditions of aluminium triiodide and carbodiimide are present, there is ether bond rupture reaction in phenyl alkyl ether, generate phenol and its derivatives at a temperature of 20 DEG C to backflow.The method mild condition, it is easy to operate, and also yield is high, and applicable phenyl alkyl ether scope is wide.
Description
Technical field
The present invention relates to medicine and the intermediate synthesis technical field of industrial chemicals, and in particular to a kind of phenyl alkyl ether
Ether bond rupture method.
Background technology
It is a kind of conventional organic reaction that phenyl alkyl ether react removing alkyl to prepare phenol by ether bond rupture.Ehter bond breaks
Splitting can be carried out in the presence of Bronsted acid or Lewis acid, and conventional Bronsted acid has HCl, HBr and HI etc., often
Lewis acid BBr3And AlCl3Deng.When substrate contains the functional group sensitive to acid, alkali, can be compared with these method demethylations
More difficult, such as eugenol can only obtain medium relatively low yield with these method demethylations.
In order to solve this problem, Lange has developed and has used AlCl3The method of-tertiary amine, and it is applied successfully to vanillic aldehyde etc.
The demethylating reaction (US3256336) of ortho-hydroxyanisole.Due to AlCl3The reactivity of The Splitting of Ether Linkage is general, for removing
The substrate of the functional group containing acid labile such as eugenol, yield is not high.Therefore, Arifin et al. has developed AlCl3- DMS sides
Method (Indon.J.Chem.2015,15,77), but for still very low (30% left side of yield of eugenol demethylating reaction
It is right).CN106278825A discloses a kind of method of use aluminium triiodide-pyridine The Splitting of Ether Linkage, is removed with approaching quantitative yield
The methyl of eugenol, but the oxytropism of aluminium triiodide is have impact on due to pyridine by the complexing with aluminium triiodide, cause this
Method is simply possible to use in o-hydroxy-phenyl alkyl ether, and cannot be used for the ether bond rupture of the phenyl alkyl ether without vicinal hydroxyl groups.
The content of the invention
To solve the problems, such as above-mentioned prior art, the invention provides a kind of ether bond rupture side of phenyl alkyl ether
Method, the method mild condition is easy to operate, and yield is high, and applicable phenyl alkyl ether scope is wide.
Realize that the technical scheme that above-mentioned purpose of the present invention is used is：
A kind of ether bond rupture method of phenyl alkyl ether, comprises the following steps：
In organic solvent, under conditions of aluminium triiodide and carbodiimide are present, phenyl alkyl ether is at -20 DEG C to backflow
At a temperature of there is ether bond rupture reaction, generate phenol and its derivatives, described phenyl alkyl ether is：
Wherein, R1、R2、R3、R4、R5Respectively：Hydrogen atom, halogen, methyl, ethyl, propyl group, isopropyl, vinyl, propylene
Base, pi-allyl, isopentene group, nitro, cyano group, carboxyl, ester group, formoxyl, acetyl group, trifluoroacetyl group, aryl, hydroxyl, first
Epoxide, ethyoxyl, isopropoxy or-OR；
The formula of described aryl is：
Described R6、R7、R8、R9、R10Respectively：Hydrogen atom, halogen, methyl, ethyl, propyl group, isopropyl, vinyl, third
Alkenyl, pi-allyl, isopentene group, nitro, cyano group, carboxyl, ester group, formoxyl, acetyl group, trifluoroacetyl group, aryl, hydroxyl,
Methoxyl group, ethyoxyl, isopropoxy or-OR；
Described R be methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, n-hexyl, n-octyl,
Dodecyl, pi-allyl, benzyl, trityl, methoxy or ethoxy.
Further, described organic solvent is any in alkane, aromatic hydrocarbons, ether, carboxylate, carbon disulfide and nitrile solvents
One or any several combination；Described alkane is petroleum ether, n-hexane, hexamethylene, hexane isomer mixture or heptan
Alkane, described aromatic hydrocarbons is benzene, toluene or dimethylbenzene, and described ether is ether, tetrahydrofuran, petroleum ether, dioxane, ethylene glycol
Dimethyl ether, diglycol dimethyl ether, triethylene-glycol dimethyl ether, methyl tertiary butyl ether(MTBE), 2- methyltetrahydrofurans or two
Phenylate, described carboxylate is Ethyl formate, propyl formate, isopropyl formate, butyl formate, iso-butyl formate, the tertiary fourth of formic acid
Ester, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, tert-butyl acetate, methyl propionate, propionic acid
Ethyl ester, propyl propionate or isopropyl propionate, described nitrile solvents are acetonitrile, propionitrile, butyronitrile, isobutyronitrile, cyanophenyl, benzene acetonitrile,
Malononitrile, succinonitrile, glutaronitrile or adiponitrile.
Further, described carbodiimide is：
Described R11、R12Respectively：Methyl, ethyl, n-propyl, isopropyl, cyclopropyl, normal-butyl, the tert-butyl group, hexamethylene
Base, trimethyl silicon substrate, benzyl, dimethylamino-propyl and its salt, 2- morpholines ethyl and its salt, phenyl, p-methylphenyl or 2,6- bis-
Isopropyl phenyl.
Further, described carbodiimide is N, N '-dicyclohexylcarbodiimide (DCC), N, and N '-diisopropyl carbon two is sub-
Amine (DIC), 1- (3- dimethylamino-propyls) -3- ethyl carbodiimides, 1- (3- dimethylamino-propyls) -3- ethyl carbodiimide salt
Hydrochlorate (EDCI), the 1- tert-butyl group -3- ethyl carbodiimides, N, N '-di-t-butyl carbodiimide, two (trimethyl silicon substrate) phosphinylidynes two
Imines, 1,3- di-p-tolyls carbon imidodicarbonic diamide, N, N'- bis- (2,6- diisopropyl phenyls) carbodiimide, 1- cyclohexyls -2-
Quinoline ethyl carbodiimide tosilate, 1,3- di-p-tolyls carbon imidodicarbonic diamide, N, N'- bis- (2,6- diisopropyl phenyls)
In carbodiimide and 1- (3- dimethyl aminopropyls) -3- ethyl carbodiimide methiodide salt any one, or any several group
Close.
Further, described carbodiimide is N, N '-dicyclohexylcarbodiimide (DCC), N, and N '-diisopropyl carbon two is sub-
Amine (DIC), 1- (3- dimethylamino-propyls) -3- ethyl carbodiimides and 1- (3- dimethylamino-propyls) -3- ethyl carbodiimides
Any one in hydrochloride (EDCI), or any several combination.
Further, the reaction time of described ether bond rupture reaction is 1 minute~48 hours.
Further, the reaction time of described ether bond rupture reaction is 1~18 hour.
Further, when phenyl alkyl ether contains the ehter bond that is urgently broken, aluminium triiodide, carbodiimide and octadecyloxy phenyl
The mol ratio of base ether is 0.4~3:0.01~10:1；When phenyl alkyl ether contains the ehter bond that multiple is urgently broken, aluminium triiodide
Consumption with carbodiimide is multiplied by the number of the ehter bond being urgently broken, such as when the ehter bond being urgently broken has two, three
The molar ratio of silver iodide, carbodiimide and phenyl alkyl ether is 0.8~6:0.02~20:1.
Further, when phenyl alkyl ether contains the ehter bond that is urgently broken, aluminium triiodide, carbodiimide and octadecyloxy phenyl
The mol ratio of base ether is 1.0~1.5:0.05~2:1.
Further, first aluminium triiodide is dissolved in organic solvent, sequentially adds carbodiimide, phenyl alkyl ether；Or first
Aluminium triiodide is dissolved in organic solvent, the mixture of carbodiimide and phenyl alkyl ether is added；Or first by carbodiimide and
Phenyl alkyl ether is added in organic solvent, adds aluminium triiodide.
Compared with prior art, advantages of the present invention is with beneficial effect：
1) present invention aluminium triiodide as ether bond rupture reagent, because it is not complexed with carbodiimide, so oxyphie
Property is unrestricted, and the reactivity of The Splitting of Ether Linkage is not influenceed by reaction condition.
2) catalysis activity of The Splitting of Ether Linkage of the present invention is higher, and the yield of reaction can reach medium to connecing with the difference of substrate
It is near quantitative.
3) present invention can use the solvent of the low polarity such as alkane, carbon disulfide, or ethyl acetate, tetrahydrofuran, second
Various types of phenyl alkyl ethers can be dissolved and be applicable by nitrile polar solvent.
4) present invention can be used for the alkyl bigger than methyl steric hindrance such as removing ethyl, isopropyl, benzyl or dodecyl.
5) functional group such as nitro, halogen, aldehyde radical, alkene, cyano group, carbonyl or carboxyl etc. is not no in o-hydroxy-phenyl alkyl ether
Influenceed by reaction condition, it is applied widely.
Specific embodiment
With reference to specific embodiment, the present invention is described in detail.
Aluminium triiodide used in following examples is bibliography (Bhatt, M.V.；Babu,
J.R.Tetrahedron Lett.1984,25,3497-3500) self-control, the detailed process that it is prepared is as follows：
To iodine, aluminium powder and acetonitrile is separately added into eggplant-shape bottle, backflow is heated to, 1 hour aubergine to iodine of stir about disappears
Lose.Room temperature is cooled to, solvent is boiled off with Rotary Evaporators, obtain the light yellow or canescence aluminium triiodide powder for preparing temporarily.
The light yellow or canescence aluminium triiodide powder glass stopper sealing that will be obtained, is put into room temperature preservation in drier, standby.
Embodiment 1 (eugenol demethylation)
To be separately added into a 100ml eggplant-shape bottle aluminium triiodide (2.247g), acetonitrile (40ml), DCC (0.618g) and
Eugenol (0.818g), is heated to 80 DEG C, and reaction stops stirring after 18 hours, is cooled to after room temperature to adding 2mol/L in eggplant-shape bottle
Watery hydrochloric acid (50ml) acidifying, with ethyl acetate (50ml × 3) extract, merge organic phase, it is first water-soluble with sodium thiosulfate saturation
Liquid (10ml) is washed, then is washed with saturated aqueous common salt (10ml), and anhydrous magnesium sulfate is dried, and filtering, filtrate is steamed with Rotary Evaporators
Dry, by rapid column chromatography, (eluent is ethyl acetate/petroleum ether=1 to residue:4, volume ratio) purifying, obtain 0.721g
4- pi-allyls catechol (white waxy solid, yield 96%).
1H NMR(400MHz,CDCl3) δ 6.80 (d, J=8Hz, 1H), 6.72 (d, J=2Hz, 1H), 6.63 (dd, J1=
8Hz,J2=2Hz, 1H), 6.10 (brs, 2H), 5.92 (ddt, J1=17.2Hz, J2=10.4Hz, J2=6.8Hz, 1H), 5.05
(dq,J1=16.8Hz, J2=1.6Hz, 1H), 5.03 (dq, J1=10.0Hz, J2=1.6Hz, 1H), 3.26 (d, J=6.4Hz,
1H)。
13C NMR(100MHz,CDCl3)δ143.35,141.54,137.65,133.60,121.33,116.09,
115.80,115.71,39.50。
Embodiment 2 (eugenol demethylation)
To being separately added into aluminium triiodide (2.252g), acetonitrile (40ml), N, N '-dicyclohexyl in a 100ml eggplant-shape bottle
Carbodiimide DCC (1.036g) and eugenol (0.818g), are heated to 80 DEG C, and reaction stops stirring after 18 hours, is cooled to room temperature
Watery hydrochloric acid (50ml) acidifying of 2mol/L is added in backward eggplant-shape bottle, is extracted with ethyl acetate (50ml × 3), merge organic phase,
First washed with thiosulfuric acid saturated aqueous solution of sodium (10ml), then washed with saturated aqueous common salt (10ml), anhydrous magnesium sulfate is dried, mistake
Filter, filtrate is evaporated with Rotary Evaporators, and by rapid column chromatography, (eluent is ethyl acetate/petroleum ether=1 to residue:4, body
Product ratio) purifying, obtain 0.723g 4- pi-allyls catechol (white waxy solid, yield 96%).
Embodiment 3 (eugenol demethylation)
To be separately added into a 100ml eggplant-shape bottle aluminium triiodide (2.247g), acetonitrile (40ml), DCC (1.549g) and
Eugenol (0.818g), is heated to 80 DEG C, and reaction stops stirring after 18 hours, is cooled to after room temperature to adding 2mol/L in eggplant-shape bottle
Watery hydrochloric acid (50ml) acidifying, with ethyl acetate (50ml × 3) extract, merge organic phase, it is first water-soluble with sodium thiosulfate saturation
Liquid (10ml) is washed, then is washed with saturated aqueous common salt (10ml), and anhydrous magnesium sulfate is dried, and filtering, filtrate is steamed with Rotary Evaporators
Dry, by rapid column chromatography, (eluent is ethyl acetate/petroleum ether=1 to residue:4, volume ratio) purifying, obtain 0.684g
4- pi-allyls catechol (white waxy solid, yield 91%).
Embodiment 4 (eugenol demethylation)
To be separately added into a 100ml eggplant-shape bottle aluminium triiodide ((2.250g), acetonitrile (40ml), DCC (2.320g) and
Eugenol (0.823g), is heated to 80 DEG C, and reaction stops stirring after 18 hours, is cooled to after room temperature to adding 2mol/L in eggplant-shape bottle
Watery hydrochloric acid (10ml) acidifying, with ethyl acetate (50ml × 3) extract, merge organic phase, it is first water-soluble with sodium thiosulfate saturation
Liquid (10ml) is washed, then is washed with saturated aqueous common salt (10ml), and anhydrous magnesium sulfate is dried, and filtering, filtrate is steamed with Rotary Evaporators
Dry, by rapid column chromatography, (eluent is ethyl acetate/petroleum ether=1 to residue:4, volume ratio) purifying, obtain 0.659g
4- pi-allyls catechol (white waxy solid, yield 87%).
Embodiment 5 (eugenol demethylation)
To be separately added into a 100ml eggplant-shape bottle aluminium triiodide (0.902g), acetonitrile (15ml), DCC (1.857g) and
Eugenol (0.328g), is heated to 80 DEG C, and reaction stops stirring after 18 hours, is cooled to after room temperature to adding 2mol/L in eggplant-shape bottle
Watery hydrochloric acid (50ml) acidifying, with ethyl acetate (50ml × 3) extract, merge organic phase, it is first water-soluble with sodium thiosulfate saturation
Liquid (10ml) is washed, then is washed with saturated aqueous common salt (10ml), and anhydrous magnesium sulfate is dried, and filtering, filtrate is steamed with Rotary Evaporators
Dry, by rapid column chromatography, (eluent is ethyl acetate/petroleum ether=1 to residue:4, volume ratio) purifying, obtain 0.283g
4- pi-allyls catechol (white waxy solid, yield 94%).
Embodiment 6 (eugenol demethylation)
To be separately added into a 100ml eggplant-shape bottle aluminium triiodide (2.252g), acetonitrile (40ml), DIC (0.636g) and
Eugenol (0.821g), is heated to 80 DEG C, and reaction stops stirring after 18 hours, is cooled to after room temperature to adding 2mol/L in eggplant-shape bottle
Watery hydrochloric acid (10ml) acidifying, with ethyl acetate (50ml × 3) extract, merge organic phase, it is first water-soluble with sodium thiosulfate saturation
Liquid (10ml) is washed, then is washed with saturated aqueous common salt (10ml), and anhydrous magnesium sulfate is dried, and filtering, filtrate is steamed with Rotary Evaporators
Dry, by rapid column chromatography, (eluent is ethyl acetate/petroleum ether=1 to residue:4, volume ratio) purifying, obtain 0.672g
4- pi-allyls catechol (white waxy solid, yield 89%).
Embodiment 7 (eugenol demethylation)
To be separately added into a 100ml eggplant-shape bottle aluminium triiodide (2.273g), acetonitrile (40ml), DIC (0.379g) and
Eugenol (0.821g), is heated to 80 DEG C, and reaction stops stirring after 18 hours, is cooled to after room temperature to adding 2mol/L in eggplant-shape bottle
Watery hydrochloric acid (10ml) acidifying, with ethyl acetate (50ml × 3) extract, merge organic phase, it is first water-soluble with sodium thiosulfate saturation
Liquid (10ml) is washed, then is washed with saturated aqueous common salt (10ml), and anhydrous magnesium sulfate is dried, and filtering, filtrate is steamed with Rotary Evaporators
Dry, by rapid column chromatography, (eluent is ethyl acetate/petroleum ether=1 to residue:4, volume ratio) purifying, obtain 0.750g
4- pi-allyls catechol (off-white color waxy solid, yield 99%).
Embodiment 8 (eugenol demethylation)
To DIC (0.378g), eugenol (0.821g) and toluene (20ml) is separately added into a 100ml eggplant-shape bottle, so
Aluminium triiodide (2.247g) is added afterwards, 80 DEG C are heated to, stirring reaction 18 hours stops stirring, be cooled to after room temperature to eggplant-shape bottle
Watery hydrochloric acid (10ml) acidifying of middle addition 2mol/L, is extracted with ethyl acetate (50ml × 3), merges organic phase, first uses thio sulphur
Sour saturated aqueous solution of sodium (10ml) washing, then washed with saturated aqueous common salt (10ml), anhydrous magnesium sulfate is dried, and filtering, filtrate is used
Rotary Evaporators are evaporated, and by rapid column chromatography, (eluent is ethyl acetate/petroleum ether=1 to residue:4, volume ratio) purifying,
Obtain 0.582g4- pi-allyls catechol (off-white color waxy solid, yield 77%).
Embodiment 9 (eugenol demethylation)
To being separately added into DIC (0.376g), eugenol (0.821g) and carbon disulfide in a 100ml eggplant-shape bottle
(40ml), is subsequently adding aluminium triiodide (2.250g), is heated to flowing back (80 DEG C of oil bath temperature), and stirring reaction 18 hours stops
Stirring, is cooled to room temperature, and carbon disulfide is boiled off with Rotary Evaporators, to watery hydrochloric acid (10ml) acid that 2mol/L is added in residue
Change, extracted with ethyl acetate (50ml × 3), merge organic phase, first washed with thiosulfuric acid saturated aqueous solution of sodium (10ml), then use
Saturated aqueous common salt (10ml) is washed, and anhydrous magnesium sulfate is dried, and filtering, filtrate is evaporated with Rotary Evaporators, and residue is by quick
(eluent is ethyl acetate/petroleum ether=1 to column chromatography:4, volume ratio) purifying, obtain 0.551g 4- pi-allyl catechols
(off-white color waxy solid, yield 73%).
Embodiment 10 (eugenol demethylation)
To being separately added into aluminium triiodide (2.246g), n-hexane (40ml), DIC (0.375g) in a 100ml eggplant-shape bottle
With eugenol (0.821g), it is heated to flowing back (80 DEG C of oil bath temperature), lamination occurs in reaction system, upper strata is clarified and lower floor
It is sticky, to addition acetonitrile (2ml) in eggplant-shape bottle, then reaction is swimmingly stirred, continue stirring reaction 1 hour, stop stirring
Mix, be acidified to the watery hydrochloric acid (10ml) of addition 2mol/L in eggplant-shape bottle after being cooled to room temperature, extracted with ethyl acetate (50ml × 3),
Merge organic phase, first washed with thiosulfuric acid saturated aqueous solution of sodium (10ml), then washed with saturated aqueous common salt (10ml), anhydrous sulphur
Sour magnesium is dried, and filtering, filtrate is evaporated with Rotary Evaporators, and by rapid column chromatography, (eluent is ethyl acetate/stone to residue
Oily ether=1:4, volume ratio) purifying, 0.642g 4- pi-allyls catechol (off-white color waxy solid, yield 85%) are obtained, and
Reclaim unreacted raw material (0.028g, 3%).
Embodiment 11 (eugenol demethylation)
To being separately added into aluminium triiodide (2.251g), tetrahydrofuran (40ml), DIC in a 100ml eggplant-shape bottle
(0.375g) and eugenol (0.821g), is heated to 80 DEG C, stirring reaction 18 hours.Triethylamine (5ml) is added, continues to stir
Reaction 2 hours, stops stirring, is acidified to the watery hydrochloric acid (10ml) of addition 2mol/L in eggplant-shape bottle after being cooled to room temperature, uses acetic acid second
Ester (50ml × 3) is extracted, and merges organic phase, is first washed with thiosulfuric acid saturated aqueous solution of sodium (10ml), then use saturated aqueous common salt
(10ml) is washed, and anhydrous magnesium sulfate is dried, and filtering, filtrate is evaporated with Rotary Evaporators, and residue passes through rapid column chromatography (drip washing
Agent is ethyl acetate/petroleum ether=1:4, volume ratio) purifying, (off-white color is wax-like solid to obtain 0.701g 4- pi-allyls catechol
Body, yield 93%).
Embodiment 12 (eugenol demethylation)
To being separately added into aluminium triiodide (2.247g), ethyl acetate (40ml), DIC in a 100ml eggplant-shape bottle
(0.375g) and eugenol (0.821g), is heated to flowing back (80 DEG C of oil bath temperature), and stirring reaction 18 hours stops stirring, cold
To adding the watery hydrochloric acid (10ml) of 2mol/L to be acidified in eggplant-shape bottle after to room temperature, extracted with ethyl acetate (50ml × 3), be associated with
Machine phase, is first washed with thiosulfuric acid saturated aqueous solution of sodium (10ml), then is washed with saturated aqueous common salt (10ml), and anhydrous magnesium sulfate is done
Dry, filtering, filtrate is evaporated with Rotary Evaporators, and by rapid column chromatography, (eluent is ethyl acetate/petroleum ether=1 to residue:
4, volume ratio) purifying, obtain 0.574g 4- pi-allyls catechol (off-white color waxy solid, yield 76%).
Embodiment 13 (eugenol demethylation)
To aluminium triiodide (2.251g), acetonitrile (40ml) is separately added into a 100ml eggplant-shape bottle, 80 DEG C are heated to, then
Disposable addition DIC (0.375g) and the mixture of eugenol (0.328g), continue to react 3 minutes after adding, and stop stirring, to
Add water (10ml) quenching reaction in eggplant-shape bottle, watery hydrochloric acid (10ml) acidifying of 2mol/L is added, with ethyl acetate (50ml × 3)
Extraction, merges organic phase, is first washed with thiosulfuric acid saturated aqueous solution of sodium (10ml), then is washed with saturated aqueous common salt (10ml),
Anhydrous magnesium sulfate is dried, and filtering, filtrate is evaporated with Rotary Evaporators, and by rapid column chromatography, (eluent is acetic acid second to residue
Ester/petroleum ether=1:4, volume ratio) purifying, obtain 0.727g 4- pi-allyls catechol (white waxy solid, yield
96%) the complete raw material (0.018g, 2%) of unreacted, is reclaimed.
Embodiment 14 (eugenol demethylation)
To aluminium triiodide (2.248g) and acetonitrile (40ml) is separately added into a 100ml eggplant-shape bottle, 80 DEG C are heated to, then
Disposable addition DIC (0.377g) and the mixture of eugenol (0.819g), continue to react 25 minutes after adding, and stop stirring,
To added water in eggplant-shape bottle (10ml) quenching reaction, add 2mol/L watery hydrochloric acid (10ml) acidifying, with ethyl acetate (50ml ×
3) extract, merge organic phase, first washed with thiosulfuric acid saturated aqueous solution of sodium (10ml), then washed with saturated aqueous common salt (10ml)
Wash, anhydrous magnesium sulfate is dried, filtering, filtrate is evaporated with Rotary Evaporators, and by rapid column chromatography, (eluent is acetic acid to residue
Ethyl ester/petroleum ether=1:4, volume ratio) purifying, obtain 0.739g 4- pi-allyls catechol (white waxy solid, yield
98%).
Embodiment 15 (eugenol demethylation)
To be separately added into a 100ml eggplant-shape bottle aluminium triiodide (2.245g), acetonitrile (40ml), EDCI (0.575g) and
Eugenol (0.820g), is heated to 80 DEG C, and reaction stops stirring after 18 hours, is cooled to after room temperature to adding 2mol/L in eggplant-shape bottle
Watery hydrochloric acid (10ml) acidifying, with ethyl acetate (50ml × 3) extract, merge organic phase, it is first water-soluble with sodium thiosulfate saturation
Liquid (10ml) is washed, then is washed with saturated aqueous common salt (10ml), and anhydrous magnesium sulfate is dried, and filtering, filtrate is steamed with Rotary Evaporators
Dry, by rapid column chromatography, (eluent is ethyl acetate/petroleum ether=1 to residue:4, volume ratio) purifying, obtain 0.621g
4- pi-allyls catechol (white solid, yield 83%).
Embodiment 16 (eugenol demethylation)
To be separately added into a 100ml eggplant-shape bottle aluminium triiodide (2.247g), acetonitrile (40ml), DIC (0.126g),
EDCI (0.384g) and eugenol (0.820g), are heated to 80 DEG C, and reaction stops stirring after 18 hours, are cooled to after room temperature to eggplant shape
Watery hydrochloric acid (10ml) acidifying of 2mol/L is added in bottle, is extracted with ethyl acetate (50ml × 3), merge organic phase, first with thio
Sulfuric acid saturated aqueous solution of sodium (10ml) is washed, then is washed with saturated aqueous common salt (10ml), and anhydrous magnesium sulfate is dried, filtering, filtrate
It is evaporated with Rotary Evaporators, by rapid column chromatography, (eluent is ethyl acetate/petroleum ether=1 to residue:4, volume ratio) it is pure
Change, obtain 0.706g 4- pi-allyls catechol (white solid, yield 94%).
Embodiment 17 (eugenol methyl ether demethylation)
To be separately added into a 100ml eggplant-shape bottle aluminium triiodide (2.248g), acetonitrile (40ml), DIC (0.126g) and
Eugenol methyl ether (0.890g), is heated to 80 DEG C, and reaction stops stirring after 18 hours, is added in eggplant-shape bottle after being cooled to room temperature
Watery hydrochloric acid (10ml) acidifying of 2mol/L, is extracted with ethyl acetate (50ml × 3), merges organic phase, first full with sodium thiosulfate
Washed with the aqueous solution (10ml), then washed with saturated aqueous common salt (10ml), anhydrous magnesium sulfate is dried, filtering, filtrate uses rotation steaming
Hair instrument is evaporated, and by rapid column chromatography, (eluent is ethyl acetate/petroleum ether=1 to residue:4, volume ratio) purifying, obtain
0.733g4- pi-allyls catechol (white waxy solid, yield 98%).
Embodiment 18 (eugenol methyl ether demethylation)
To be separately added into a 100ml eggplant-shape bottle aluminium triiodide (2.253g), acetonitrile (40ml), DIC (0.380g) and
Eugenol methyl ether (0.891g), is heated to 80 DEG C, and reaction stops stirring after 18 hours, is added in eggplant-shape bottle after being cooled to room temperature
Watery hydrochloric acid (10ml) acidifying of 2mol/L, is extracted with ethyl acetate (50ml × 3), merges organic phase, first full with sodium thiosulfate
Washed with the aqueous solution (10ml), then washed with saturated aqueous common salt (10ml), anhydrous magnesium sulfate is dried, filtering, filtrate uses rotation steaming
Hair instrument is evaporated, and by rapid column chromatography, (eluent is ethyl acetate/petroleum ether=1 to residue:4, volume ratio) purifying, obtain
0.742g 4- pi-allyls catechol (white waxy solid, yield 99%).
Embodiment 19 (eugenol methyl ether demethylation)
To be separately added into a 100ml eggplant-shape bottle aluminium triiodide (1.797g), acetonitrile (40ml), DCC (1.856g) and
Eugenol methyl ether (0.714g), is heated to 80 DEG C, and reaction stops stirring after 18 hours, is added in eggplant-shape bottle after being cooled to room temperature
Watery hydrochloric acid (10ml) acidifying of 2mol/L, is extracted with ethyl acetate (50ml × 3), merges organic phase, first full with sodium thiosulfate
Washed with the aqueous solution (10ml), then washed with saturated aqueous common salt (10ml), anhydrous magnesium sulfate is dried, filtering, filtrate uses rotation steaming
Hair instrument is evaporated, and by rapid column chromatography, (eluent is ethyl acetate/petroleum ether=1 to residue:4, volume ratio) purifying, obtain
0.590g 4- pi-allyls catechol (white waxy solid, yield 98%).
Embodiment 20 (isoeugenol demethylation)
To be separately added into a 100ml eggplant-shape bottle aluminium triiodide (2.252g), acetonitrile (40ml), DIC (0.379g) and
Isoeugenol (0.821g), is heated to 80 DEG C, and reaction stops stirring after 18 hours, is added in eggplant-shape bottle after being cooled to room temperature
Watery hydrochloric acid (10ml) acidifying of 2mol/L, is extracted with ethyl acetate (50ml × 3), merges organic phase, first full with sodium thiosulfate
Washed with the aqueous solution (10ml), then washed with saturated aqueous common salt (10ml), anhydrous magnesium sulfate is dried, filtering, filtrate uses rotation steaming
Hair instrument is evaporated, and by rapid column chromatography, (eluent is ethyl acetate/petroleum ether=1 to residue:4, volume ratio) purifying, obtain
0.708g 4- acrylic catechol (white waxy solid, yield 94%).
1H NMR(400MHz,CDCl3) δ 6.86 (s, 2H), 6.79-6.74 (m, 2H), 6.25 (d, J=15.6Hz, 1H),
6.08-5.99 (m, 1H), 5.40 (brs, 2H), 1.83 (d, J=6.4Hz, 3H).
13C NMR(100MHz,CDCl3)δ143.45,142.44,131.84,130.23,124.05,119.13,
115.46,112.56,18.34。
Embodiment 21 (dehydrodimerization eugenol demethylation)
To be separately added into a 100ml eggplant-shape bottle aluminium triiodide (2.252g), acetonitrile (40ml), DIC (0.379g) and
Dehydrodimerization eugenol (0.808g), is heated to 80 DEG C, and reaction stops stirring after 18 hours, adds in eggplant-shape bottle after being cooled to room temperature
Enter watery hydrochloric acid (10ml) acidifying of 2mol/L, extracted with ethyl acetate (50ml × 3), merge organic phase, first use sodium thiosulfate
Saturated aqueous solution (10ml) is washed, then is washed with saturated aqueous common salt (10ml), and anhydrous magnesium sulfate is dried, filtering, filtrate rotation
Evaporimeter is evaporated, and by rapid column chromatography, (eluent is ethyl acetate/petroleum ether=1 to residue:4, volume ratio) purifying, obtain
0.585g dehydrodimerizations [(4- pi-allyls)-catechol] (white solid, yield 79%).
1H NMR(400MHz,CD3Cl)δ6.79(s,2H),6.71(s,2H),6.12(brs,2H),5.97(ddt,J1=
16.8Hz,J2=10.0Hz, J3=6.4Hz, 2H), 5.58 (brs, 2H), 5.10 (d, J=16.8Hz, 2H), 5.07 (d, J=
9.2Hz, 2H), 3.33 (d, J=6.8Hz, 4H).
13C NMR(101MHz,CD3Cl)δ144.68,138.42,137.31,133.97,124.86,122.29,
115.93,114.96,39.66。
Embodiment 22 (vanillic aldehyde demethylation)
To be separately added into a 100ml eggplant-shape bottle aluminium triiodide (2.250g), acetonitrile (40ml), DIC (0.380g) and
Vanillic aldehyde (0.761g), is heated to 80 DEG C, and reaction stops stirring after 18 hours, is cooled to after room temperature to adding 2mol/L in eggplant-shape bottle
Watery hydrochloric acid (10ml) acidifying, with ethyl acetate (50ml × 3) extract, merge organic phase, it is first water-soluble with sodium thiosulfate saturation
Liquid (10ml) is washed, then is washed with saturated aqueous common salt (10ml), and anhydrous magnesium sulfate is dried, and filtering, filtrate is steamed with Rotary Evaporators
Dry, by rapid column chromatography, (eluent is ethyl acetate/petroleum ether=1 to residue:1, volume ratio) purifying, 0.654g3 is obtained,
4- 4-dihydroxy benzaldehydes (white solid, yield 94%).
1H NMR(400MHz,d6-DMSO)δ10.11(brs,1H),9.70(s,1H),9.55(brs,1H),7.27(dd,
J1=8.0Hz, J2=2.0Hz, 1H), 7.23 (d, J=1.6Hz, 1H), 7.06 (s, 1H), 6.91 (d, J=8.0Hz, 1H).
13C NMR(100MHz,d6-DMSO)δ191.59,152.59,146.33,129.31,125.03,115.97,
114.78。
Embodiment 23 (isovanillin demethylation)
To be separately added into a 100ml eggplant-shape bottle aluminium triiodide (2.247g), acetonitrile (40ml), DIC (0.378g) and
Isovanillin (0.759g), is heated to 80 DEG C, and reaction stops stirring after 18 hours, is added in eggplant-shape bottle after being cooled to room temperature
Watery hydrochloric acid (10ml) acidifying of 2mol/L, is extracted with ethyl acetate (50ml × 3), merges organic phase, first full with sodium thiosulfate
Washed with the aqueous solution (10ml), then washed with saturated aqueous common salt (10ml), anhydrous magnesium sulfate is dried, filtering, filtrate uses rotation steaming
Hair instrument is evaporated, and by rapid column chromatography, (eluent is ethyl acetate/petroleum ether=1 to residue:1, volume ratio) purifying, obtain
0.649g3,4- 4-dihydroxy benzaldehyde (white solid, yield 94%).
Embodiment 24 (Ethyl vanillin takes off ethyl)
To be separately added into a 100ml eggplant-shape bottle aluminium triiodide (2.248g), acetonitrile (40ml), DIC (0.375g) and
Ethyl vanillin (0.832g), is heated to 80 DEG C, and reaction stops stirring after 18 hours, is added in eggplant-shape bottle after being cooled to room temperature
Watery hydrochloric acid (10ml) acidifying of 2mol/L, is extracted with ethyl acetate (50ml × 3), merges organic phase, uses sodium thiosulfate saturation
The aqueous solution (10ml) is washed, then is washed with saturated aqueous common salt (10ml), and anhydrous magnesium sulfate is dried, filtering, filtrate rotary evaporation
Instrument is evaporated, and by rapid column chromatography, (eluent is ethyl acetate/petroleum ether=1 to residue:1, volume ratio) purifying, obtain
0.567g3,4- 4-dihydroxy benzaldehyde (white solid, yield 82%).
Embodiment 25 (vanillone demethylation)
To be separately added into a 100ml eggplant-shape bottle aluminium triiodide (2.250g), acetonitrile (40ml), DIC (0.378g) and
Vanillone (0.831g), is heated to 80 DEG C, and reaction stops stirring after 18 hours, is cooled to after room temperature to adding 2mol/L in eggplant-shape bottle
Watery hydrochloric acid (10ml) acidifying, with ethyl acetate (50ml × 3) extract, merge organic phase, it is first water-soluble with sodium thiosulfate saturation
Liquid (10ml) is washed, then is washed with saturated aqueous common salt (10ml), and anhydrous magnesium sulfate is dried, and filtering, filtrate is steamed with Rotary Evaporators
Dry, by rapid column chromatography, (eluent is ethyl acetate/petroleum ether=3 to residue:7, volume ratio) purifying, 0.496g3 is obtained,
4- resacetophenones (white solid, yield 65%).
1H NMR(400MHz,d6- DMSO) δ 9.57 (brs, 2H), 7.34 (d, J=8.0Hz, 1H), 7.33 (s, 1H),
6.80 (d, J=8.0Hz, 1H), 2.43 (s, 3H).
13C NMR(100MHz,d6-DMSO)δ196.67,151.08,145.56,129.43,122.15,115.47,
115.36,26.64。
Embodiment 26 (4- hydroxy 3-methoxybenzene nitriles demethylation)
To be separately added into a 100ml eggplant-shape bottle aluminium triiodide (2.253g), acetonitrile (40ml), DIC (0.378g) and
4- hydroxy 3-methoxybenzenes nitrile (0.742g), are heated to 80 DEG C, and reaction stops stirring after 18 hours, are cooled to after room temperature to eggplant shape
Watery hydrochloric acid (10ml) acidifying of 2mol/L is added in bottle, is extracted with ethyl acetate (50ml × 3), merge organic phase, first with thio
Sulfuric acid saturated aqueous solution of sodium (10ml) is washed, then is washed with saturated aqueous common salt (10ml), and anhydrous magnesium sulfate is dried, filtering, filtrate
It is evaporated with Rotary Evaporators, by rapid column chromatography, (eluent is ethyl acetate/petroleum ether=3 to residue:7, volume ratio) it is pure
Change, obtain 0.636g4- cyano group catechol (white solid, yield 94%).
1H NMR(400MHz,d6- DMSO) δ 9.96 (brs, 1H), 9.90 (brs, 1H), 7.11 (d, J=8.4Hz, 1H),
7.06 (s, 1H), 6.86 (d, J=8.4Hz, 1H).
13C NMR(100MHz,d6-DMSO)δ150.99,146.36,125.24,120.04,118.81,116.78,
101.36。
Embodiment 27 (3- hydroxyl -4- methoxy cyanophenyls demethylation)
To be separately added into a 100ml eggplant-shape bottle aluminium triiodide (2.250g), acetonitrile (40ml), DIC (0.378g) and
3- hydroxyl -4- methoxy cyanophenyls (0.743g), is heated to 80 DEG C, and reaction stops stirring after 18 hours, is cooled to after room temperature to eggplant shape
Watery hydrochloric acid (10ml) acidifying of 2mol/L is added in bottle, is extracted with ethyl acetate (50ml × 3), merge organic phase, first with thio
Sulfuric acid saturated aqueous solution of sodium (10ml) is washed, then is washed with saturated aqueous common salt (10ml), and anhydrous magnesium sulfate is dried, filtering, filtrate
It is evaporated with Rotary Evaporators, by rapid column chromatography, (eluent is ethyl acetate/petroleum ether=1 to residue:1.5, volume ratio)
Purifying, obtains 0.658g4- cyano group catechol (white solid, yield 98%).
Embodiment 28 (vanillic acid demethylation)
To be separately added into a 100ml eggplant-shape bottle aluminium triiodide (2.253g), acetonitrile (40ml), DIC (0.379g) and
Vanillic acid (0.838g), is heated to 80 DEG C, and reaction stops stirring after 18 hours, is cooled to after room temperature to adding 2mol/L in eggplant-shape bottle
Watery hydrochloric acid (10ml) acidifying, with ethyl acetate (50ml × 3) extract, merge organic phase, it is first water-soluble with sodium thiosulfate saturation
Liquid (10ml) is washed, then is washed with saturated aqueous common salt (10ml), and anhydrous magnesium sulfate is dried, and filtering, filtrate is steamed with Rotary Evaporators
It is dry, residue from dichloromethane (50ml) washing, then drained to constant weight with oil pump, obtain 0.768g protocatechuic acid (white solid,
Yield 100%).
1H NMR(400MHz,d6-DMSO)δ12.32(brs,1H),9.67(brs,1H),9.33(brs,1H),7.33(d,
J=2.0Hz, 1H), 7.06 (s, 1H), 7.28 (dd, J1=8.0Hz, J2=2.0Hz, 1H), 6.78 (d, J=8.0Hz, 1H).
13C NMR(100MHz,d6-DMSO)δ167.80,150.44,145.31,122.39,122.09,116.98,
115.61。
Embodiment 29 (vanillic acid methyl esters demethylation)
To be separately added into a 100ml eggplant-shape bottle aluminium triiodide (2.247g), acetonitrile (40ml), DIC (0.380g) and
Vanillic acid methyl esters (0.910g), are heated to 80 DEG C, and reaction stops stirring after 18 hours, is added in eggplant-shape bottle after being cooled to room temperature
Watery hydrochloric acid (10ml) acidifying of 2mol/L, is extracted with ethyl acetate (50ml × 3), merges organic phase, uses sodium thiosulfate saturation
The aqueous solution (10ml) is washed, then is washed with saturated aqueous common salt (10ml), and anhydrous magnesium sulfate is dried, filtering, filtrate rotary evaporation
Instrument is evaporated, and by rapid column chromatography, (eluent is ethyl acetate/petroleum ether=3 to residue:2, volume ratio) purifying, obtain
0.684g protocatechuic acid (white solid, yield 89%) and a small amount of protocatechuic acid methyl esters.
1H NMR(400MHz,d6- DMSO) δ 9.58 (brs, 2H), 7.36 (s, 1H), 7.32 (d, J=8.4Hz, 1H),
6.81 (d, J=8.4Hz, 1H), 3.76 (s, 3H).
13C NMR(100MHz,d6-DMSO)δ166.62,150.86,145.52,122.23,120.97,116.74,
115.77,52.02。
Embodiment 30 (vanillic acid methyl esters demethylation)
To being separately added into aluminium triiodide (2.247g), acetonitrile (40ml) DIC (0.378g) and perfume in a 100ml eggplant-shape bottle
Methyl oxalate (0.909g), is heated to 40 DEG C, and reaction stops stirring after 18 hours, is added in eggplant-shape bottle after being cooled to room temperature
Watery hydrochloric acid (10ml) acidifying of 2mol/L, is extracted with ethyl acetate (50ml × 3), merges organic phase, first full with sodium thiosulfate
Washed with the aqueous solution (10ml), then washed with saturated aqueous common salt (10ml), anhydrous magnesium sulfate is dried, filtering, filtrate uses rotation steaming
Hair instrument is evaporated, and residue (is ethyl acetate/petroleum ether=3 by rapid column chromatography:7, volume ratio) purifying, obtain 0.260g former
Catechuic acid methyl esters (white solid, yield 31%) and unreacted raw material (2mg).The polarity of eluent is increased into acetic acid second
Ester/petroleum ether=1:1 (volume ratio), obtains 0.496g protocatechuic acid (white solid, yield 64%).
Embodiment 31 (guaiacol demethylation)
To be separately added into a 100ml eggplant-shape bottle aluminium triiodide (2.252g), acetonitrile (40ml), DIC (0.380g) and
Guaiacol (0.623g), is heated to 80 DEG C, and reaction stops stirring after 18 hours, is added in eggplant-shape bottle after being cooled to room temperature
Watery hydrochloric acid (10ml) acidifying of 2mol/L, is extracted with ethyl acetate (50ml × 3), merges organic phase, first full with sodium thiosulfate
Washed with the aqueous solution (10ml), then washed with saturated aqueous common salt (10ml), anhydrous magnesium sulfate is dried, filtering, filtrate uses rotation steaming
Hair instrument is evaporated, and by rapid column chromatography, (eluent is ethyl acetate/petroleum ether=1 to residue:4, volume ratio) purifying, obtain
0.497g catechols (white solid, yield 90%).
1H NMR(400MHz,CDCl3)δ6.90-6.85(m,2H),6.84-6.79(m,2H),5.23(brs,2H)。
13C NMR(100MHz,CDCl3)δ143.48,121.31,115.53。
Embodiment 32 (guaiacol demethylation)
To be separately added into a 250ml eggplant-shape bottle aluminium triiodide (4.492g), acetonitrile (80ml), DIC (0.634g) and
Guaiacol (1.242g), is heated to 80 DEG C, and reaction stops stirring after 18 hours, is added in eggplant-shape bottle after being cooled to room temperature
Watery hydrochloric acid (10ml) acidifying of 2mol/L, is extracted with ethyl acetate (100ml × 3), merges organic phase, first full with sodium thiosulfate
Washed with the aqueous solution (15ml), then washed with saturated aqueous common salt (10ml), anhydrous magnesium sulfate is dried, filtering, filtrate uses rotation steaming
Hair instrument is evaporated, and by rapid column chromatography, (eluent is ethyl acetate/petroleum ether=1 to residue:4, volume ratio) purifying, obtain
1.024g catechols (white waxy solid, yield 93%).
Embodiment 33 (o-isopropoxyphenol takes off isopropyl)
To be separately added into a 100ml eggplant-shape bottle aluminium triiodide (2.253g), acetonitrile (40ml), DIC (0.376g) and
O-isopropoxyphenol (0.758g), is heated to 80 DEG C, and reaction stops stirring after 18 hours, adds in eggplant-shape bottle after being cooled to room temperature
Enter watery hydrochloric acid (10ml) acidifying of 2mol/L, extracted with ethyl acetate (50ml × 3), merge organic phase, first use sodium thiosulfate
Saturated aqueous solution (10ml) is washed, then is washed with saturated aqueous common salt (10ml), and anhydrous magnesium sulfate is dried, filtering, filtrate rotation
Evaporimeter is evaporated, and by rapid column chromatography, (eluent is ethyl acetate/petroleum ether=1 to residue:4, volume ratio) purifying, obtain
0.520g catechols (white solid, yield 94%).
Embodiment 34 (meta-methoxy phenol demethylation)
To be separately added into a 100ml eggplant-shape bottle aluminium triiodide (2.252g), acetonitrile (40ml), DIC (0.387g) and
Meta-methoxy phenol (0.621g), is heated to 80 DEG C, and reaction stops stirring after 18 hours, is added in eggplant-shape bottle after being cooled to room temperature
Watery hydrochloric acid (10ml) acidifying of 2mol/L, is extracted with ethyl acetate (50ml × 3), merges organic phase, first full with sodium thiosulfate
Washed with the aqueous solution (10ml), then washed with saturated aqueous common salt (10ml), anhydrous magnesium sulfate is dried, filtering, filtrate uses rotation steaming
Hair instrument is evaporated, and by rapid column chromatography, (eluent is ethyl acetate/petroleum ether=1 to residue:3, volume ratio) purifying, obtain
0.523g resorcinols (white solid, yield 95%).
1H NMR(400MHz,d6- DMSO) δ 9.23 (s, 2H), 6.92 (t, J=8.0Hz, 1H), 6.20 (s, 1H), 6.19
(d, J=7.3Hz, 1H).
13C NMR(100MHz,d6-DMSO)δ158.85,130.20,106.69,102.93。
Embodiment 35 (the bromo- 5- hydroxyls -4-methoxybenzaldehyde demethylations of 2-)
To be separately added into a 100ml eggplant-shape bottle aluminium triiodide (2.250g), acetonitrile (40ml), DIC (0.378g) and
The bromo- 5- hydroxyls of 2- -4-methoxybenzaldehyde (1.156g), are heated to 80 DEG C, and reaction stops stirring after 18 hours, after being cooled to room temperature
To adding the watery hydrochloric acid (10ml) of 2mol/L to be acidified in eggplant-shape bottle, extracted with ethyl acetate (50ml × 3), merge organic phase, used
Thiosulfuric acid saturated aqueous solution of sodium (10ml) is washed, then is washed with saturated aqueous common salt (10ml), and anhydrous magnesium sulfate is dried, filtering,
Filtrate is evaporated with Rotary Evaporators, and by rapid column chromatography, (eluent is ethyl acetate/petroleum ether=1 to residue:4, volume
Than) purifying, obtain bromo- 4, the 5- 4-dihydroxy benzaldehydes of 0.666g2- (yellow solid, yield 61%).
1H NMR(400MHz,d6-DMSO)δ10.21(brs,2H),9.95(s,1H),7.25(s,H),7.05(s,1H)。
13C NMR(100MHz,d6-DMSO)δ190.44,153.55,146.14,125.27,120.02,117.45,
115.57。
Embodiment 36 (4- allyl benzene methyl ethers demethylation)
To be separately added into a 100ml eggplant-shape bottle aluminium triiodide (2.248g), acetonitrile (40ml), DIC (0.130g) and
4- allyl benzenes methyl ether (0.741g), are heated to 80 DEG C, and reaction stops stirring after 18 hours, adds in eggplant-shape bottle after being cooled to room temperature
Enter watery hydrochloric acid (10ml) acidifying of 2mol/L, extracted with ethyl acetate (50ml × 3), merge organic phase, first use sodium thiosulfate
Saturated aqueous solution (10ml) is washed, then is washed with saturated aqueous common salt (10ml), and anhydrous magnesium sulfate is dried, filtering, filtrate rotation
Evaporimeter is evaporated, and by rapid column chromatography, (eluent is ethyl acetate/petroleum ether=1 to residue:4, volume ratio) purifying, obtain
0.670g4- chavicols (pale yellowish oil liquid, yield 100%).
1H NMR(400MHz,CDCl3) δ 7.05 (d, J=7.8Hz, 2H), 6.76 (d, J=7.6Hz, 2H), 5.94 (ddt,
J1=16.8Hz, J2=10.0Hz, J2=6.6Hz, 1H), 5.05 (d, J=16.8Hz, 1H), 5.04 (d, J=10.0Hz, 1H),
4.92 (brs, 1H), 3.31 (d, J=6.6Hz, 2H).
13C NMR(100MHz,CDCl3)δ153.74,137.85,132.32,129.74,115.50,115.27,39.34。
Embodiment 37 (4- allyl benzene methyl ethers demethylation)
To be separately added into a 100ml eggplant-shape bottle aluminium triiodide (0.818g), acetonitrile (40ml), DIC (0.133g) and
4- allyl benzenes methyl ether (0.743g), are heated to 80 DEG C, and reaction stops stirring after 18 hours, adds in eggplant-shape bottle after being cooled to room temperature
Enter watery hydrochloric acid (10ml) acidifying of 2mol/L, extracted with ethyl acetate (50ml × 3), merge organic phase, first use sodium thiosulfate
Saturated aqueous solution (10ml) is washed, then is washed with saturated aqueous common salt (10ml), and anhydrous magnesium sulfate is dried, filtering, filtrate rotation
Evaporimeter is evaporated, and by rapid column chromatography, (eluent is ethyl acetate/petroleum ether=1 to residue:4, volume ratio) purifying, obtain
0.497g4- chavicols (pale yellowish oil liquid, yield 73%).
Embodiment 38 (4- allyl benzene methyl ethers demethylation)
To be separately added into a 100ml eggplant-shape bottle aluminium triiodide (2.250g), acetonitrile (40ml), DIC (0.378g) and
4- allyl benzenes methyl ether (0.744g), are heated to 80 DEG C, react 18 hours, stop stirring, add in eggplant-shape bottle after being cooled to room temperature
Enter watery hydrochloric acid (10ml) acidifying of 2mol/L, extracted with ethyl acetate (50ml × 3), merge organic phase, first use sodium thiosulfate
Saturated aqueous solution (10ml) is washed, then is washed with saturated aqueous common salt (10ml), and anhydrous magnesium sulfate is dried.Filtering, filtrate rotation
Evaporimeter is evaporated, and by rapid column chromatography, (eluent is ethyl acetate/petroleum ether=1 to residue:4, volume ratio) purifying, obtain
0.615g 4- chavicols (pale yellowish oil liquid, yield 91%).
Embodiment 39 (synthetic capsaicin demethylation)
To be separately added into a 100ml eggplant-shape bottle aluminium triiodide (2.248g), acetonitrile (40ml), DIC (0.380g) and
Synthetic capsaicin (1.467g), is heated to 80 DEG C, and reaction stops stirring after 18 hours, is added in eggplant-shape bottle after being cooled to room temperature
Watery hydrochloric acid (10ml) acidifying of 2mol/L, is extracted with ethyl acetate (50ml × 3), merges organic phase, first full with sodium thiosulfate
Washed with the aqueous solution (10ml), then washed with saturated aqueous common salt (10ml), anhydrous magnesium sulfate is dried.Filtering, filtrate is steamed with rotation
Hair instrument is evaporated, and by rapid column chromatography, (eluent is ethyl acetate/petroleum ether=1 to residue:1, volume ratio) purifying, obtain
1.304gN- (3,4- dihydroxy benzyl) pelargonamide (yellow solid, yield 93%).
1H NMR(400MHz,CDCl3) δ 8.57 (brs, 1H), 6.83 (s, 1H), 6.80 (d, J=8.0Hz, 1H), 6.61
(d, J=8.0Hz, 1H), 6.28 (brs, 1H), 6.00 (t, J=6.4Hz, 1H), 4.30 (d, J=5.6Hz, 2H), 2.21 (t, J
=8.0Hz, 2H), 1.61 (quint, J=7.2Hz, 2H), 1.33-1.17 (m, 10H), 0.86 (t, J=6.4Hz, 3H).
13C NMR(100MHz,CDCl3)δ174.29,144.63,144.32,129.95,119.75,114.83,
114.77,77.22,43.54,36.86,31.78,29.22,29.10,25.78,22.63,14.09。
Embodiment 40 (O-VANILLIN demethylation)
To be separately added into a 100ml eggplant-shape bottle aluminium triiodide (2.252g), acetonitrile (40ml), DIC (0.378g) and
O-VANILLIN (0.758g), is heated to 80 DEG C, reacts 48 hours, stops stirring, is cooled to after room temperature to adding 2mol/ in eggplant-shape bottle
Watery hydrochloric acid (10ml) acidifying of L, is extracted with ethyl acetate (50ml × 3), merges organic phase, first water-soluble with sodium thiosulfate saturation
Liquid (10ml) is washed, then is washed with saturated aqueous common salt (10ml), and anhydrous magnesium sulfate is dried, and filtering, filtrate is steamed with Rotary Evaporators
Dry, by rapid column chromatography, (eluent is ethyl acetate/petroleum ether=1 to residue:3, volume ratio) purifying, obtain 2,3- dihydroxies
Benzaldehyde (yellow solid, 0.442g, yield 64%).Fusing point:106℃.
1H NMR(400MHz,d6- DMSO) δ 10.20 (s, 1H), 10.11 (s, 1H), 9.82 (s, 1H), 7.13 (d, J=
8.0Hz, 1H), 7.07 (d, J=8.0Hz, 1H), 6.79 (t, J=8.0Hz, 1H).
13C NMR(100MHz,d6-DMSO)δ193.28,150.17,146.59,123.15,121.69,120.07,
119.78。
Embodiment 41 (O-VANILLIN demethylation)
To be separately added into a 100ml eggplant-shape bottle aluminium triiodide (2.253g), acetonitrile (40ml), DIC (0.383g) and
O-VANILLIN (0.763g), is heated to 80 DEG C, reacts 8 hours, stops stirring, is cooled to after room temperature to adding 2mol/L in eggplant-shape bottle
Watery hydrochloric acid (10ml) acidifying, with ethyl acetate (50ml × 3) extract, merge organic phase, it is first water-soluble with sodium thiosulfate saturation
Liquid (10ml) is washed, then is washed with saturated aqueous common salt (10ml), and anhydrous magnesium sulfate is dried, and filtering, filtrate is steamed with Rotary Evaporators
Dry, by rapid column chromatography, (eluent is ethyl acetate/petroleum ether=1 to residue:3, volume ratio) purifying, 0.450g2 is obtained,
3- 4-dihydroxy benzaldehydes (yellow solid, yield 65%).
Embodiment 42 (6- formoxyl eugenols demethylation)
To be separately added into a 100ml eggplant-shape bottle aluminium triiodide (0.897g), acetonitrile (10ml), DIC (0.120g) and
The mixture of 6- formoxyls eugenol (0.380g), is heated to 80 DEG C, and reaction stops stirring after 18 hours, is cooled to after room temperature to eggplant
Watery hydrochloric acid (10ml) acidifying of 2mol/L is added in shape bottle, is extracted with ethyl acetate (50ml × 3), merge organic phase, first use sulphur
Sodium thiosulfate saturated aqueous solution (10ml) is washed, then is washed with saturated aqueous common salt (10ml), and anhydrous magnesium sulfate is dried, filtering, filter
Liquid is evaporated with Rotary Evaporators, and by rapid column chromatography, (eluent is ethyl acetate/petroleum ether=1 to residue:9, volume ratio)
Purifying, obtains 0.144g6- formoxyl -4- pi-allyls catechol (light yellow solid, yield 40%).Rf=0.54 (oil
Ether/ethyl acetate=3:1, volume ratio).
1H NMR(400MHz,CDCl3)δ10.95(s,1H),9.86(s,1H),7.05(s,1H),6.96(s,1H),
6.08-5.79 (m, 1H), 5.63 (s, 1H), 5.23-4.97 (m, 2H), 3.35 (d, J=6.7Hz, 2H).
13C NMR(100MHz,CDCl3)δ196.72,146.73,144.71,136.66,132.29,123.70,
122.13,120.28,116.52,39.20。
Embodiment 43 (5- nitro vanillins demethylation)
To aluminium triiodide (2.248g), acetonitrile (40ml) is separately added into a 100ml eggplant-shape bottle, backflow is heated to, then
DIC (0.378g) and 5- nitro vanillins (0.986g) are sequentially added, 80 DEG C are heated to, reaction stops stirring after 18 hours, cold
To adding the watery hydrochloric acid (10ml) of 2mol/L to be acidified in eggplant-shape bottle after to room temperature, extracted with ethyl acetate (50ml × 3), be associated with
Machine phase, is first washed with thiosulfuric acid saturated aqueous solution of sodium (10ml), then is washed with saturated aqueous common salt (10ml), and anhydrous magnesium sulfate is done
Dry, filtering, filtrate is evaporated with Rotary Evaporators, and by rapid column chromatography, (eluent is ethyl acetate/petroleum ether=2 to residue:
3, volume ratio) purifying, obtain 0.395g 3,4- dihydroxy -5- nitrobenzaldehydes (yellow solid, yield 43%).
1H NMR(400MHz,d6-DMSO)δ10.96(brs,2H),9.81(s,1H),7.98(s,H),7.47(s,1H)。
13C NMR(100MHz,d6-DMSO)δ191.03,148.77,147.74,137.70,127.35,120.15,
116.10。
Embodiment 44 (4- nitro -2- metoxyphenols demethylation)
To be separately added into a 100ml eggplant-shape bottle aluminium triiodide (2.251g), acetonitrile (40ml), DIC (0.375g) and
The mixture of 4- nitro -2- metoxyphenols (0.848g), is heated to 80 DEG C, and reaction stops stirring after 18 hours, is cooled to room temperature
Watery hydrochloric acid (10ml) acidifying of 2mol/L is added in backward eggplant-shape bottle, is extracted with ethyl acetate (50ml × 3), merge organic phase,
First washed with thiosulfuric acid saturated aqueous solution of sodium (10ml), then washed with saturated aqueous common salt (10ml), anhydrous magnesium sulfate is dried, mistake
Filter, filtrate is evaporated with Rotary Evaporators, and by rapid column chromatography, (eluent is ethyl acetate/petroleum ether=3 to residue:7, body
Product ratio) purifying, obtain 0.165g4- pi-allyls catechol (yellow solid, yield 21%).Rf=0.80 (petroleum ether/acetic acid
Ethyl ester=1:1, volume ratio).
1H NMR(400MHz,d6- DMSO) δ 10.50 (brs, 1H), 10.13 (brs, 1H), 7.63 (d, J=8.8Hz,
1H), 7.60 (s 1H), 6.89 (d, J=8.8Hz, 1H).
13C NMR(100MHz,d6-DMSO)δ153.33,145.90,139.90,116.98,115.46,110.84。
Embodiment 45 (2- allyl phenyl benzylic ethers debenzylation)
To addition 2- chavicols (1.335g), potassium carbonate (2.803g), benzyl chloride in a 100ml eggplant-shape bottle
(1.500g) and acetonitrile (40ml), is heated to 80 DEG C, and stirring reaction 18 hours stops stirring, after being cooled to room temperature, by gained
Mix products are poured into water (50ml), are extracted with ethyl acetate (50ml × 3), merge organic phase, first use sodium thiosulfate saturation
The aqueous solution (10ml) is washed, then is washed with saturated aqueous common salt (10ml), and anhydrous magnesium sulfate is dried, filtering, filtrate rotary evaporation
Instrument is evaporated, and by rapid column chromatography, (eluent is ethyl acetate/petroleum ether=1 to residue:19, volume ratio) purifying, obtain
2.195g2- allyl phenyls benzylic ether (colourless oil liquid, yield 98%).
1H NMR(100MHz,CDCl3) δ 7.44 (d, J=7.6Hz, 2H), 7.38 (d, J=7.6Hz, 2H), 7.31 (t, J
=6.8Hz, 1H), 7.18 (t, J=6.8Hz, 2H), 6.92 (t, J=7.6Hz, 2H), 6.02 (ddt, J1=16.8Hz, J2=
10.4Hz,J3=6.8Hz, 1H), 5.08 (s, 2H), 5.08-5.03 (m, 2H), 3.45 (d, J=6.4Hz, 2H).
13C NMR(100MHz,CDCl3)δ156.35,137.41,137.00,129.91,129.03,128.53,
127.78,127.33,127.13,120.83,115.53,111.69,69.88,34.52。
To be separately added into a 100ml eggplant-shape bottle aluminium triiodide (1.538g), acetonitrile (40ml), DIC (0.042g) and
2- allyl phenyls benzylic ether (0.761g), are heated to 80 DEG C, and reaction stops stirring after 18 hours, are cooled to after room temperature to eggplant-shape bottle
Watery hydrochloric acid (10ml) acidifying of middle addition 2mol/L, is extracted with ethyl acetate (50ml × 3), merges organic phase, first uses thio sulphur
Sour saturated aqueous solution of sodium (10ml) washing, then washed with saturated aqueous common salt (10ml), anhydrous magnesium sulfate is dried, and filtering, filtrate is used
Rotary Evaporators are evaporated, and by rapid column chromatography, (eluent is ethyl acetate/petroleum ether=1 to residue:4, volume ratio) purifying,
Obtain 0.314g2- chavicols (pale yellowish oil liquid, yield 68%).Rf=0.67 (petrol ether/ethyl acetate=3:
1,v/v).
1H NMR(400MHz,CDCl3) δ 7.18-7.08 (m, 2H), 6.89 (t, J=7.4Hz, 1H), 6.81 (d, J=
7.9Hz,1H),6.02(ddt,J1=17.2Hz, J2=10.4Hz, J3=6.4Hz, 1H), 5.21-5.11 (m, 2H), 5.08
(brs, 1H), 3.41 (d, J=6.4Hz, 2H).
13C NMR(100MHz,CDCl3)δ154.09,136.42,130.49,127.95,125.30,121.00,
116.56,115.83,35.17。
Embodiment 46 (2- allyl phenyls lauryl ether takes off dodecyl)
To addition 2- chavicols (1.344g), potassium carbonate (2.895g), bromododecane in a 100ml eggplant-shape bottle
(2.648g) and acetonitrile (40ml), is heated to 80 DEG C, and stirring reaction 18 hours stops stirring, is cooled to room temperature, by the mixed of gained
Close product to pour into water (50ml), extracted with ethyl acetate (50ml × 3), merge organic phase, first use sodium thiosulfate saturation water
Solution (10ml) is washed, then is washed with saturated aqueous common salt (10ml), and anhydrous magnesium sulfate is dried, filtering, filtrate Rotary Evaporators
It is evaporated, by rapid column chromatography, (eluent is ethyl acetate/petroleum ether=1 to residue:19, volume ratio) purifying, obtain
2.879g2- allyl phenyls lauryl ether (colourless oil liquid, yield 95%).
1H NMR(100MHz,CDCl3) δ 7.15 (t, J=8.0Hz, 1H), 7.13 (d, J=7.6Hz, 1H), 6.87 (t, J
=7.6Hz, 1H), 6.82 (d, J=8.0Hz, 1H), 5.99 (ddt J1=16.8Hz, J2=10.0Hz, J3=6.8Hz, 1H),
5.06 (d, J=16.4Hz, 1H), 5.02 (d, J=10.8Hz, 1H), 3.94 (t, J=6.4Hz, 2H), 3.39 (d, J=
6.8Hz, 2H), 1.78 (qui, J=6.8Hz, 2H), 1.46 (qui, J=6.8Hz, 2H), 1.40-1.20 (m, 16H), 0.88
(t, J=6.4Hz, 3H).
13C NMR(100MHz,CDCl3)δ156.77,137.17,129.69,128.78,127.26,120.26,
115.30,111.13,67.90,34.54,32.00,29.76,29.73,29.69,29.46,29.43,26.24,22.77,
14.20。
To be separately added into a 100ml eggplant-shape bottle aluminium triiodide (2.144g), acetonitrile (40ml), DIC (0.149g) and
2- allyl phenyls lauryl ether (1.445g), are heated to 80 DEG C, and reaction stops stirring after 18 hours, are cooled to after room temperature to eggplant
Watery hydrochloric acid (10ml) acidifying of 2mol/L is added in shape bottle, is extracted with ethyl acetate (50ml × 3), merge organic phase, first use sulphur
Sodium thiosulfate saturated aqueous solution (10ml) is washed, then is washed with saturated aqueous common salt (10ml), and anhydrous magnesium sulfate is dried, filtering, filter
Liquid is evaporated with Rotary Evaporators, and by rapid column chromatography, (eluent is ethyl acetate/petroleum ether=1 to residue:4, volume ratio)
Purifying, obtains 0.201g2- chavicols (pale yellowish oil liquid, yield 31%).
Embodiment 47 (2- allyl phenyl pi-allyl bases ether takes off pi-allyl)
To addition 2- chavicols (1.341g), potassium carbonate (2.806g), allyl bromide, bromoallylene in a 100ml eggplant-shape bottle
(1.904g) and acetonitrile (40ml), is heated to 80 DEG C, and stirring reaction 18 hours stops stirring, is cooled to room temperature, by the mixed of gained
Close product to pour into water (50ml), extracted with ethyl acetate (50ml × 3), merge organic phase, first use sodium thiosulfate saturation water
Solution (10ml) is washed, then is washed with saturated aqueous common salt (10ml), and anhydrous magnesium sulfate is dried, filtering, filtrate Rotary Evaporators
It is evaporated, by rapid column chromatography, (eluent is ethyl acetate/petroleum ether=1 to residue:19, volume ratio) purifying, obtain
1.425g 2- allyl phenyl pi-allyl bases ether (colourless oil liquid, yield 81%).
1H NMR(100MHz,CDCl3) δ 7.20-7.13 (m, 2H), 6.90 (t, J=6.4Hz, 1H), 6.83 (d, J=
8.0Hz, 1H), 6.11-5.95 (m, 2H), 5.43 (d, J=17.2Hz), 5.26 (d, J=10.8Hz, 1H), 5.07 (d, J=
17.2Hz, 1H), 5.03 (d, J=9.6Hz, 1H), 4.54 (d, J=4.4Hz, 2H), 3.42 (d, J=6.8Hz, 2H).
13C NMR(100MHz,CDCl3)δ156.21,137.01,133.54,129.85,128.96,127.25,
120.71,116.90,115.43,111.63,68.72,34.46。
To be separately added into a 100ml eggplant-shape bottle aluminium triiodide (3.567g), acetonitrile (40ml), DIC (0.098g) and
2- allyl phenyls allyl ether (1.386g), are heated to 80 DEG C, and reaction stops stirring after 18 hours, are cooled to after room temperature to eggplant shape
Watery hydrochloric acid (10ml) acidifying of 2mol/L is added in bottle, is extracted with ethyl acetate (50ml × 3), merge organic phase, use thio sulphur
Sour saturated aqueous solution of sodium (10ml) washing, then washed with saturated aqueous common salt (10ml), anhydrous magnesium sulfate is dried, and filtering, filtrate is used
Rotary Evaporators are evaporated, and by rapid column chromatography, (eluent is ethyl acetate/petroleum ether=1 to residue:4, volume ratio) purifying,
Obtain 0.878g2- chavicols (pale yellowish oil liquid, yield 82%).
Claims (10)
1. a kind of ether bond rupture method of phenyl alkyl ether, it is characterised in that comprise the following steps：
In organic solvent, under conditions of aluminium triiodide and carbodiimide are present, phenyl alkyl ether is in -20 DEG C of temperature to backflow
Degree is lower to there is ether bond rupture reaction, generates phenol and its derivatives, and described phenyl alkyl ether is：
Wherein, R1、R2、R3、R4、R5Respectively：Hydrogen atom, halogen, methyl, ethyl, propyl group, isopropyl, vinyl, acrylic,
Pi-allyl, isopentene group, nitro, cyano group, carboxyl, ester group, formoxyl, acetyl group, trifluoroacetyl group, aryl, hydroxyl, methoxy
Base, ethyoxyl, isopropoxy or-OR；
The formula of described aryl is：
Described R6、R7、R8、R9、R10Respectively：Hydrogen atom, halogen, methyl, ethyl, propyl group, isopropyl, vinyl, propylene
Base, pi-allyl, isopentene group, nitro, cyano group, carboxyl, ester group, formoxyl, acetyl group, trifluoroacetyl group, aryl, hydroxyl, first
Epoxide, ethyoxyl, isopropoxy or-OR；
Described R is methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, n-hexyl, n-octyl, positive ten
Dialkyl group, pi-allyl, benzyl, trityl, methoxy or ethoxyl methyl.
2. the ether bond rupture method of phenyl alkyl ether according to claim 1, it is characterised in that：Described organic solvent is
Any one in alkane, aromatic hydrocarbons, ether, carboxylate, carbon disulfide and nitrile solvents, or any several combination；Described
Alkane is petroleum ether, n-hexane, hexamethylene, hexane isomer mixture or heptane, and described aromatic hydrocarbons is benzene, toluene or diformazan
Benzene, described ether is ether, tetrahydrofuran, dioxane, glycol dimethyl ether, diglycol dimethyl ether, two three second of contracting
Glycol dimethyl ether, methyl tertiary butyl ether(MTBE), 2- methyltetrahydrofurans or diphenyl ether, described carboxylate are Ethyl formate, formic acid third
Ester, isopropyl formate, butyl formate, iso-butyl formate, t-butyl formate, ethyl acetate, propyl acetate, isopropyl acetate, second
Acid butyl ester, isobutyl acetate, tert-butyl acetate, methyl propionate, ethyl propionate, propyl propionate or isopropyl propionate, described nitrile
Class solvent is acetonitrile, propionitrile, butyronitrile, isobutyronitrile, cyanophenyl, benzene acetonitrile, malononitrile, succinonitrile, glutaronitrile or adiponitrile.
3. the ether bond rupture method of phenyl alkyl ether according to claim 1, it is characterised in that described carbodiimide is：
Described R11、R12Respectively：Methyl, ethyl, n-propyl, isopropyl, cyclopropyl, normal-butyl, the tert-butyl group, cyclohexyl, three
Methylsilyl, benzyl, dimethylamino-propyl and its salt, 2- morpholines ethyl and its salt, phenyl, p-methylphenyl or 2,6- diisopropyls
Phenyl.
4. the ether bond rupture method of phenyl alkyl ether according to claim 3, it is characterised in that：Described carbodiimide is
N, N '-dicyclohexylcarbodiimide, N, N '-DIC, 1- (3- dimethylamino-propyls) -3- ethyls carbon two are sub-
Amine, 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides, the 1- tert-butyl group -3- ethyl carbodiimides, N, the uncles of N '-two
Butyl carbodiimide, two (trimethyl silicon substrate) phosphinylidyne diimines, 1,3- di-p-tolyls carbon imidodicarbonic diamide, the N, (2,6- bis- of N'- bis-
Isopropyl phenyl) carbodiimide, 1- cyclohexyl -2- morpholine ethyl carbodiimides tosilate, 1,3- di-p-tolyl carbon
Imidodicarbonic diamide, N, (2,6- diisopropyl phenyls) carbodiimides of N'- bis- and 1- (3- dimethyl aminopropyls) -3- ethyl carbodiimides
In methiodide salt any one, or any several combination.
5. the ether bond rupture method of phenyl alkyl ether according to claim 4, it is characterised in that：Described carbodiimide is
N, N '-dicyclohexylcarbodiimide, N, N '-DIC, 1- (3- dimethylamino-propyls) -3- ethyl carbodiimides
With any one in 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides, or any several combination.
6. the ether bond rupture method of phenyl alkyl ether according to claim 1, it is characterised in that：Described ether bond rupture is anti-
The reaction time answered is 1 minute~48 hours.
7. the ether bond rupture method of phenyl alkyl ether according to claim 6, it is characterised in that：Described ether bond rupture is anti-
The reaction time answered is 0.5~18 hour.
8. the ether bond rupture method of phenyl alkyl ether according to claim 1, it is characterised in that：When phenyl alkyl ether contains
During one ehter bond being urgently broken, the mol ratio of aluminium triiodide, carbodiimide and phenyl alkyl ether is 0.4~3:0.01~10:
1；When phenyl alkyl ether contains the ehter bond that multiple is urgently broken, the consumption of aluminium triiodide and carbodiimide is by the ether being urgently broken
The number of key is multiplied.
9. the ether bond rupture method of phenyl alkyl ether according to claim 8, it is characterised in that：When phenyl alkyl ether contains
During one ehter bond being urgently broken, the mol ratio of aluminium triiodide, carbodiimide and phenyl alkyl ether is 1.0~1.5:0.05~
2:1。
10. the ether bond rupture method of phenyl alkyl ether according to claim 1, it is characterised in that：
First aluminium triiodide is dissolved in organic solvent, carbodiimide, phenyl alkyl ether is sequentially added；Or it is first that aluminium triiodide is molten
In organic solvent, the mixture of carbodiimide and phenyl alkyl ether is added；Or first add carbodiimide and phenyl alkyl ether
Enter in organic solvent, add aluminium triiodide.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107473916A (en) * | 2017-08-10 | 2017-12-15 | 荆楚理工学院 | A kind of ether bond rupture method of phenyl alkyl ether |
| CN108516925A (en) * | 2018-05-24 | 2018-09-11 | 荆楚理工学院 | A kind of ehter bond cleavage method of phenyl alkyl ether |
| CN108821955A (en) * | 2018-05-24 | 2018-11-16 | 荆楚理工学院 | A method of the methyl by removing O-VANILLIN prepares 2,3- 4-dihydroxy benzaldehyde |
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| CN111454132A (en) * | 2020-03-31 | 2020-07-28 | 江西恒诚天然香料油有限公司 | Method for synthesizing eugenol |
| CN111454133A (en) * | 2020-03-31 | 2020-07-28 | 江西恒诚天然香料油有限公司 | Synthesis method of eugenol |
| CN111620764A (en) * | 2020-03-24 | 2020-09-04 | 荆楚理工学院 | Selective ether bond breaking method of aryl alkyl ether |
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| CN106278825A (en) * | 2016-08-12 | 2017-01-04 | 荆楚理工学院 | A kind of ether bond rupture method of o-hydroxy-phenyl alkyl ether |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106278825A (en) * | 2016-08-12 | 2017-01-04 | 荆楚理工学院 | A kind of ether bond rupture method of o-hydroxy-phenyl alkyl ether |
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| CN107473916A (en) * | 2017-08-10 | 2017-12-15 | 荆楚理工学院 | A kind of ether bond rupture method of phenyl alkyl ether |
| CN107473916B (en) * | 2017-08-10 | 2020-09-22 | 荆楚理工学院 | Ether bond breaking method of phenyl alkyl ether |
| CN108516925A (en) * | 2018-05-24 | 2018-09-11 | 荆楚理工学院 | A kind of ehter bond cleavage method of phenyl alkyl ether |
| CN108821955A (en) * | 2018-05-24 | 2018-11-16 | 荆楚理工学院 | A method of the methyl by removing O-VANILLIN prepares 2,3- 4-dihydroxy benzaldehyde |
| CN108821955B (en) * | 2018-05-24 | 2021-05-18 | 荆楚理工学院 | Method for preparing 2, 3-dihydroxybenzaldehyde by removing methyl of o-vanillin |
| CN108516925B (en) * | 2018-05-24 | 2021-05-18 | 荆楚理工学院 | Ether bond cracking method of phenyl alkyl ether |
| CN110256205A (en) * | 2019-06-28 | 2019-09-20 | 常熟理工学院 | The method of nickel catalytic eliminating olefines protecting group |
| CN110256205B (en) * | 2019-06-28 | 2022-02-11 | 常熟理工学院 | Method for removing olefin protective group by nickel catalysis |
| CN111620764A (en) * | 2020-03-24 | 2020-09-04 | 荆楚理工学院 | Selective ether bond breaking method of aryl alkyl ether |
| CN111620764B (en) * | 2020-03-24 | 2023-05-05 | 荆楚理工学院 | Selective ether bond cleavage method of aryl alkyl ether |
| CN111454132A (en) * | 2020-03-31 | 2020-07-28 | 江西恒诚天然香料油有限公司 | Method for synthesizing eugenol |
| CN111454133A (en) * | 2020-03-31 | 2020-07-28 | 江西恒诚天然香料油有限公司 | Synthesis method of eugenol |
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